CN1148819C - Nickel hydroxide positive active material for alkali battery and electrode using the same - Google Patents
Nickel hydroxide positive active material for alkali battery and electrode using the same Download PDFInfo
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- CN1148819C CN1148819C CNB991060377A CN99106037A CN1148819C CN 1148819 C CN1148819 C CN 1148819C CN B991060377 A CNB991060377 A CN B991060377A CN 99106037 A CN99106037 A CN 99106037A CN 1148819 C CN1148819 C CN 1148819C
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 160
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 15
- 239000003513 alkali Substances 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 102
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 97
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 48
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 39
- 239000010941 cobalt Substances 0.000 claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 abstract description 24
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 abstract description 22
- -1 cobalt oxyhydroxide Chemical compound 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 4
- 239000011149 active material Substances 0.000 description 45
- 208000028659 discharge Diseases 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- 238000003860 storage Methods 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000008213 purified water Substances 0.000 description 9
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A nickel hydroxide positive active material for an alkaline battery contains nickel hydroxide powder having a nickel valence of greater than 2 and a cobalt compound having a cobalt valence of greater than 2 which is formed on the surface of the said nickel hydroxide powder. For example, the surface of nickel oxyhydroxide powder is covered by cobalt oxyhydroxide layer. This positive active material is used as a original material to produce an electrode by retaining it in a three-dimensional porous material.
Description
Technical Field
The present invention relates to a nickel hydroxide positive active material for an alkaline battery and a nickel hydroxide electrode using the same.
Technical Field
Nickel hydroxide electrodes containing a compound mainly composed of nickel hydroxide as an active material have been used as positive electrodes of alkaline batteries such as nickel-cadmium storage batteries and nickel-metal hydride storage batteries. Such alkaline storage batteries are used as power sources for small portable electronic devices. To improve these electronic devices, high-capacity alkaline storage batteries are desired. For this reason, the nickel hydroxide electrode for controlling the discharge capacity of the alkaline storage battery must have a high energy density.
As a nickel hydroxide electrode, a sintered electrode has been used so far. A sintered electrode is prepared by sintering nickel powder on a porous stamped metal to obtain a substrate, and then impregnating the substrate with a nickel hydroxide active material. However, such a nickel hydroxide electrode has a defect that the porosity of the substrate is about 80%, and thus itis difficult to impregnate a large amount of active material. Therefore, such a substrate is not suitable for the improvement of the energy density of the nickel hydroxide electrode.
On the other hand, a non-sintered nickel hydroxide electrode obtained by retaining a nickel hydroxide active material in a substrate of a three-dimensional porous metal material such as foamed nickel or fibrous nickel, has a porosity of the substrate of not less than 95%. Therefore, this electrode is suitable for increasing the energy density of the nickel hydroxide electrode as compared with the above sintered nickel hydroxide electrode. Under these conditions, studies for improving the capacity of alkaline storage batteries have been conducted mainly using non-sintered nickel hydroxide electrodes.
The non-sintered nickel hydroxide electrode exhibits low conductivity of nickel hydroxide. Therefore, it is necessary to incorporate ｃA cobalt compound such as cobalt hydroxide, cobalt monoxide and cobaltous monoxide or metallic cobalt as ｃA conductive agent in the nickel hydroxide electrode or coat the surface of the nickel hydroxide particles with ｃA cobalt compound or metallic compound as disclosed in JP-A-62-117267 (the term "JP-A" as used herein means an "unexamined Japanese patent publication").
It is considered that the added cobalt compound is converted into cobalt oxyhydroxide having high conductivity by electrochemical oxidation during the first charge. A conductive network is then formed in the electrode, acting as an effective conductive agent in the nickel hydroxide electrode. The coating on the surface of the nickel hydroxide particles can improve the contact area of the cobalt compound and the nickel hydroxide, and compared with the simple addition of the cobalt compound, the effect of improving the utilization percentage of the active material is increased.
Nickel hydroxide, which is used as an active material of a nickel hydroxide electrode in an alkaline storage battery, is oxidized during charging to form nickel oxyhydroxide. And is reduced to nickel hydroxide during discharge. Nickel hydroxide is a material having lower electrical conductivity than nickel oxyhydroxide. Therefore, the nickel hydroxide has a drawback in that it causes a decrease in charging efficiency at the initial stage of charging, particularly during the first charging for formation.
To solve these problems, ｃA method of uniformly adding nickel oxyhydroxide, which is ｃA material having higher electrical conductivity than nickel hydroxide, to ｃA nickel hydroxide electrode material before preparing ｃA nickel hydroxide electrode as described in JP-A-2-262245 and JP-A-2-234356 has been proposed.
However, it was found that the discharge capacity obtained by adding nickel oxyhydroxide to a nickel hydroxide electrode having a conventional cobalt compound such as cobalt hydroxide and cobalt monoxide or metallic cobalt having a cobalt valence of 2 or less, which is incorporated into the electrode, is smaller than that calculated.
It is an object of the present invention to provide an improved nickel hydroxide active material for alkaline batteries and a nickel hydroxide electrode using the improved nickel hydroxide active material.
Disclosure of Invention
The inventors studied the causes of the above phenomenon. As a result, it was concluded that a cobalt compound having a cobalt valence of not more than 2 (even if part of the cobalt has a cobalt valence of more than 2 but is lower than the valence of the nickel hydroxide having a valence of more than 2) is partially oxidized by an orthonickel hydroxide having a high oxidizing ability to form a high-valence cobalt compound, resulting in poor distribution of the cobalt compound in the nickel hydroxide electrode and insufficient formation of an orthocobalt hydroxide conductive network, which is considered to be necessary for maintaining the conductivity of the nickel hydroxide electrode. From this conclusion, it was found that the formation of the above-mentioned cobalt oxyhydroxide on the surface of nickel hydroxide particles can solve the above-mentioned problems. The inventors have also discovered during the research a method of increasing the discharge capacity of alkaline cells.
The present invention provides a nickel hydroxide positive electrode active material for alkaline batteries, which is characterized in that a cobalt compound having a valence of cobalt of more than 2 is formed on the surface of a powder mainly composed of nickel hydroxide having a valence of nickel of more than 2.3.
According to the present invention, the electrode is composed of a three-dimensional porous material in which the above-described nickel hydroxide positive electrode active material is held.
According to the present invention, the utilization percentage of the active material in the nickel hydroxide electrode can be increased, so that a high-capacity alkaline battery can be provided.
Drawings
FIG. 1 is a graph illustrating discharge performance of an embodiment of a nickel-cadmium battery according to the present invention; and
fig. 2 is a graph illustrating discharge performance of another embodiment of a nickel-metal hydride battery according to the invention.
Detailed Description
The nickel hydroxide positive active material of the alkaline battery according to the present invention mainly includes nickel hydroxide powder having a nickel valence of more than 2. A cobalt compound having a cobalt valence of more than 2 is formed on the surface of the nickel hydroxide powder. The nickel hydroxide powder of the present invention has an average particle diameter in the range of 7 to 30 μm, preferably about 10 μm. The average particle size includes the thickness of the cobalt compound formed on the surface of the particles.
The nickel hydroxide electrode according to the present invention is composed of a three-dimensional porous material that retains the above-described nickel hydroxide positive electrode active material therein.
The nickel hydroxide powder according to the present invention mainly comprises nickel hydroxide having a nickel valence of more than 2. If the nickel valence of the nickel hydroxide powder exceeds 3, gamma-nickel oxyhydroxide is produced, which is considered to have an adverse effect on the charge-discharge cycle life of the alkaline storage battery. Therefore, the nickel valence of the nickel hydroxide used as the main component is preferably not more than 3.
The cobalt compound formed on the surface of the nickel hydroxide powder having a nickel valence of more than 2 preferably covers the nickel hydroxide powder in a layered form. If the cobalt valence of the cobalt compound is smaller than the nickel valence of the nickel hydroxide powder, the cobalt compound can be easily oxidized due to the strong oxidizing ability of the nickel hydroxide powder, which makes it difficult to maintain its conductivity. Therefore, the cobalt valence of the cobalt compound is preferably equal to or greater than the nickel valence of the nickel hydroxide powder. In other words, the cobalt compound is one of the materials that determine the electrical conductivityof the nickel hydroxide powder serving as an active material. Therefore, the cobalt compound preferably has high conductivity. It is preferable that the nickel hydroxide powder has an average nickel valence not exceeding an average cobalt valence of a cobalt compound having a cobalt valence of more than 2 covering the nickel hydroxide powder.
The three-dimensional porous material is preferably a three-dimensional porous metal material such as foamed nickel and fibrous nickel.
Further, the nickel hydroxide electrode according to the present invention is preferably composed of a mixture of first nickel hydroxide powder having a nickel valence of not more than 2 and a cobalt valence of a cobalt compound formed on a surface thereof of more than 2 and second nickel hydroxide powder having a nickel valence of more than 2 and a cobalt valence of a cobalt compound formed on a surface thereof of more than 2, and a three-dimensional porous material holding the mixture. In particular, the average nickel valence of the mixture of the first and second nickel oxyhydroxide powders held in the three-dimensional porous material is preferably not less than 2.07.
This is because when the average nickel valence of the entire nickel hydroxide active material containing nickel hydroxide is not more than 2.07, nickel hydroxide having a nickel valence of more than 2 shows a decrease in the effect of improving conductivity.
The nickel hydroxide positive electrode of the present invention is mainly composed of a nickel hydroxide powder, and is characterized in that a cobalt compound having a valence of more than 2 is formed on the surface of a powder mainly composed of a nickel hydroxide having a valence of more than 2.3.
The nickel hydroxide active material, which is the main component of the powder of the present invention, has a nickel valence ofgreater than 2. Therefore, the powder according to the present invention has higher electrical conductivity than the conventional nickel hydroxide powder. Furthermore, since the cobalt compound having a cobalt valence greater than 2 formed on the surface of the nickel hydroxide powder also has high electrical conductivity, a nickel hydroxide electrode having high electrical conductivity can be prepared using the nickel hydroxide powder of the present invention, thereby increasing the utilization percentage of the nickel hydroxide electrode of an alkaline battery.
The nickel hydroxide active material of the alkaline cell according to the present invention can be used as a positive electrode active material of an alkaline cell, particularly an alkaline storage battery. The nickel hydroxide powder for alkaline batteries according to the present invention can be used alone as an active material. On the other hand, the nickel hydroxide powder for alkaline batteries according to the present invention can be used in admixture with an active material made of a powder mainly composed of nickel hydroxide, the active material being prepared by forming cobalt oxyhydroxide on the surface of nickel hydroxide particles, that is, forming a cobalt compound having a cobalt valence of more than 2 on the surface of the powder. The mixture also includes other active materials or additives entrained therein. In particular, the nickel hydroxide powder of the present invention can be used in the form of a mixture with a nickel hydroxide powder having a nickel valence of not more than 2 but having a cobalt compound having a cobalt valence of more than 2 on the surface thereof, so that it is easy to control the nickel valence in the nickel hydroxide active material of the positive electrode.
Also, the active material of the present invention can be used as a raw material of an electrode. The active material of the present invention is preferably held on a three-dimensional porous support to prepare an electrode.
Examples
The present invention will be further described in the following examples and comparative examples.
(example 1)
The nickel hydroxide powder was dispersed in purified water in an amount three times the weight of the powder. The aqueous dispersion was then adjusted with 23% by weight aqueous sodium hydroxide solution to a weakly basic pH of 11. Then, an aqueous solution of cobalt sulfate was dropped into the aqueous dispersion under stirring in an inert gas atmosphere to prepare an active material made of nickel hydroxide in which 10 wt% of cobalt hydroxide was covered on the surface of the nickel hydroxide powder. Subsequently, the alkaline suspension containing the active material is evacuated in air. The extracted suspension is heated to 80 ℃, stirred for 3 hours, washed and then dried to obtain the nickel hydroxide coated by the cobalt compound with the valence of more than 2. The sample is then subjected to chemical analysis. As a result, the cobalt compound coating layer was cobalt oxyhydroxide having a cobalt valence of 3.0. The nickel valence of the nickel hydroxide powder is 2.0.
330g (nickel hydroxide content: 3.24 moles) of the above nickel hydroxide covered with cobalt oxyhydroxide was dispersed in 5000cc of a 5 wt% aqueous sodium hydroxide solution at room temperature. 231g (about 0.98 mol) of sodium peroxodisulfate as an oxidizing agent was then added to the dispersion with stirring, causing a reaction according to the following reaction equation (1). After stirring for 10 hours, the reaction product was washed and dried to obtain active material powder a.
As a result, it was found that the cobalt valence of the active material powder a was 3.0 and the nickel valence was 2.5.
Then, a paste sample was prepared using 100 parts by weight of the resultant active material powder a, 1 part by weight of carboxymethyl cellulose and purified water. The foamed nickel substrate was impregnated with the prepared paste sample, pressed, and then dried to obtain a nickel hydroxide electrode a made of the active material powder a of the present invention.
For the negative electrode, a well-known cadmium negative plate is used, and the preparation process is as follows: by applying a paste sample consisting essentially of 70 parts by weight of cadmium oxide powder and 30 parts by weight of metallic cadmium powder to punching metal, drying the punching metal, and then pressing the punching metal.
Then, 3 sheets of the prepared positive electrode plate, 4 sheets of the obtained negative electrode plate and a hydrophilic treated polyolefin separator were used to form an element. The formed element was inserted into a battery case filled with an electrolyte solution composed mainly of an aqueous potassium hydroxide solution. Then, a lid with a safety valve was welded to the battery can to obtain battery a of the present invention containing active material powder a of the present invention.
Comparative example 1
A paste sample was prepared using 100 parts by weight of nickel hydroxide coated with cobalt oxyhydroxide as a precursor of the active material powder a of the present invention, 1 part by weight of carboxymethyl cellulose, and purified water. The paste sample was used to impregnate a foamed nickel substrate, pressed, and then dried to prepare a nickel hydroxide electrode B. A comparative battery B was obtained in the same manner as in example 1, except that the prepared nickel hydroxide electrode B was used.
Comparative example 2
200g (about 2.16 moles) of nickel hydroxide powder was dispersed in 2 liters of 5 wt% aqueous sodium hydroxide solution. 309g (about 1.30 mol) of sodium peroxodisulfate as an oxidizing agent was then added to the above dispersion with stirring to cause a reaction according to the following reaction equation (1). After stirring for 10 hours, the reaction product was washed and dried to obtain active material powder C.
The chemical analysis result revealed that the nickel valence of the obtained active material powder C was 3.0. the X-ray diffraction analysis result showed that the active material powder C was composed of β -nickel oxyhydroxide.
The resultant active material powder C and nickel hydroxide powder covered with 10 wt% of cobalt oxyhydroxide were then dry-blended in a weight ratio of 45: 50. A paste sample was prepared using 100 parts by weight of the mixed powder, 1 part by weight of carboxymethyl cellulose, and purified water. The foamed nickel substrate was impregnated with the prepared paste sample, pressed, and then dried to obtain a nickel hydroxide electrode C composed of active material powder C. A comparative cell C was prepared in the same manner as in example 1, except that the prepared nickel hydroxide electrode C was used.
The theoretical capacity of the positive electrodes of all these batteries is 1000 mAh. These batteries are prepared with a capacity-excess negative electrode, so that the positive electrode functions as a capacity-defining electrode during charge and discharge.
Each of these batteries was subjected to 10 cycles of 12-hour charging at 100mA and discharging to 0.8V at 100mA at 25 ℃, and then the discharge capacity was measured under the following conditions:
charging.. 200mA 120% (6 hours) under
200mA to 0.8V
25 deg.C
The measurement results are shown in fig. 1. The discharge capacity of the battery a of the present invention using an active material consisting essentially of nickel hydroxide having a valence of 2.5 coated with cobalt oxyhydroxide was about 1030 mAh. On the other hand, comparative cell B using nickel hydroxide coated with cobalt oxyhydroxide and comparative cell C using nickel oxyhydroxide powder and nickel hydroxide powder coated with cobalt oxyhydroxide had discharge capacities of about 980mAh and 1000mAh, respectively.
The discharge capacities of the batteries a and C using nickel oxyhydroxide in the positive electrode thereof were larger than that of the comparative battery B without nickel oxyhydroxide. This is presumably due to the inclusion of nickel oxyhydroxide in the positive electrode resulting in an increase in the conductivity of the active material itself, increasing the percent utilization of the active material.
The reason why the battery a of the present invention using an active material mainly composed of nickel hydroxide coated with cobalt oxyhydroxide having a nickel valence of 2.5 has a larger discharge capacity than the comparative battery C using nickel oxyhydroxide and nickel hydroxide coated with cobalt oxyhydroxide is presumably that the battery a of the present invention uses a nickel hydroxide powder uniformly coated with cobalt oxyhydroxide and can maintain its conductivity even at the final stage of discharge.
The embodiments have been described with reference to a nickel-cadmium battery having a cadmium electrode as the negative electrode. However, other alkaline storage batteries using a zinc electrode or a metal hydride electrode as the negative electrode can also obtain similar effects.
The nickel hydroxide active material of the present invention exhibits similar effects when it contains at least one element selected from the group consisting of cobalt, manganese, zinc, cadmium and calcium dissolved in a solid phase therein in addition to single-component particles composed of only a nickel compound.
(example 2)
The nickel hydroxide powder was dispersed in purified water in an amount three times the weight of the powder. The aqueous dispersion was then adjusted to a pH of 11 by adding 23% by weight aqueous potassium hydroxide solution. The dispersion liquid was stirred while dropping an aqueous solution of cobalt sulfate into the above aqueous dispersion liquid under an inert gas atmosphere to produce a nickel hydroxide active material, i.e., a nickel hydroxide powder whose surface was covered with 10 wt% of cobalt hydroxide relative to nickel hydroxide. Subsequently, the alkaline suspension containing the active material is evacuated in air. The withdrawn suspension was stirred at a temperature of 80 ℃ for 3 hours. Thereafter, washing is performed, followed by drying, to obtain nickel hydroxide covered with a cobalt compound having a cobalt valence of more than 2. The sample is then subjected to chemical analysis. As a result, the cobalt valence of the cobalt compound coating layer was 3.0. The nickel valence of the nickel hydroxide powder is 2.0.
Thereafter, the nickel hydroxide powder coated with the cobalt compound having a valence greater than 2 and the potassium peroxodisulfate powder were dispersed in a 26 wt% aqueous potassium hydroxide solution (the amount of the aqueous potassium hydroxide solution was about 20 times that of the nickel hydroxide powder coated with the cobalt compound having a valence greater than 2) at a molar ratio of 2: 1.4 to cause a reaction according to the following reaction equation (1). The reaction solution was then stirred at room temperature for 10 hours. After the reaction, the dispersion was filtered to obtain a black powder. The resulting black powder was washed with purified water until the PH of the washing water reached 7, and then dried to obtain nickel oxyhydroxide powder coated with a cobalt compound having a valence greater than 2. The resulting nickel oxyhydroxide powder was chemically analyzed in the same manner as described above. As a result, it was found that the nickel valence of the nickel oxyhydroxide powder was 3.0 and the cobalt valence was 3.0. In this example, the valence of the cobalt cladding layer before oxidation was 3. Thus, the cobalt coating is not believed to be oxidized by potassium peroxodisulfate.
Then, 85 parts by weight of the above nickel hydroxide powder coated with a cobalt compound having a cobalt valence of 3, 15 parts by weight of nickel oxyhydroxide powder coated with a cobalt compound having a cobalt valence of 3, and 2 parts by weight of carboxymethyl cellulose were added to purified water to prepare a paste sample. The prepared paste sample was used to impregnate a foamed nickel substrate, pressed, and then dried to obtain a nickel hydroxide electrode D of the present invention. The average nickel valence of the resulting nickel hydroxide electrode D was then measured. As a result, the average valence of the nickel hydroxide electrode D was found to be 2.15.
For the negative electrode, the preparation process of the used plate is as follows: the coated punched metal was dried by applying a paste sample consisting essentially of a known AB5 type hydrogen absorbing alloy to the punched metal, and then pressing the punched metal.
Then, 3 prepared positive electrode plates, 4 prepared negative electrode plates, and a hydrophilic treated polyolefin separator were used to form one element. The formed element was inserted into a battery case filled with an electrolyte solution composed mainly of an aqueous potassium hydroxide solution. Then, a lid with a safety valve was welded to the battery can to obtain battery D of the invention.
Comparative example 3
The nickel hydroxide powder was dispersed in purified water about three times the weight of the powder. A23% by weight aqueous potassium hydroxide solution was then added to the aqueous dispersion to adjust the pH to 11. The dispersion liquid was stirred while dropping an aqueous solution of cobalt sulfate into the aqueous dispersion liquid under an inert gas atmosphere, and then a nickel hydroxide active material was obtained, i.e., a nickel hydroxide powder whose surface was covered with 11.3 wt% of cobalt hydroxide relative to nickel hydroxide. Subsequently, the alkaline suspension containing the active material is evacuated in air. The withdrawn suspension was stirred at a temperature of 80 ℃ for 3 hours. Thereafter, washing is performed, followed by drying, to obtain a nickel hydroxide powder coated with a cobalt compound having a cobalt valence of more than 2. The sample is then subjected to chemical analysis. As a result, the cobalt valence of the cobalt compound coating layer was 3.0. The nickel valence of the nickel hydroxide powder is 2.0.
A nickel hydroxide electrode E was then prepared in the same manner as in the above example of the nickel hydroxide electrode D, except that 88.5 parts by weight of a nickel hydroxide powder coated with a cobalt compound having a cobalt valence greater than 2 and 11.5 parts by weight of an nickel oxyhydroxide powder were used. A nickel hydroxide electrode E was used to obtain a comparative cell E. The average nickel valence of the resulting nickel hydroxide electrode E was then measured. As a result, it was found that the average nickel valence of the nickel hydroxide electrode E was 2.15.
Comparative example 4
10 parts by weight of cobalt hydroxide powder, 90 parts by weight of nickel hydroxide powder and 2 parts by weight of carboxymethyl cellulose powder were added to purified water to prepare a paste sample. The foamed nickel substrate was impregnated with the prepared paste sample, pressed, and then dried to obtain a nickel hydroxide electrode F. A comparative battery F was prepared in the same manner as in the above example except for the above conditions. The average nickel valence of the resulting nickel hydroxide electrode F was then measured. As a result, the average nickel valence of the nickel hydroxide electrode F was found to be 2.00.
The theoretical capacity of the positive electrode of all these cells was 1000 mAh.
Each of these batteries was subjected to 10 cycles of charging at 100mA for 12 hours and discharging at 100mA to 0.8V at room temperature to completely activate the hydrogen absorbing alloy negative electrode, and then the discharge capacity was measured under the following conditions:
charging.. 200mA 120% (6 hours) under
200mA to 0.8V
25 deg.C
The measurement results are shown in fig. 2. Battery D of the present invention has a discharge capacity of about 1030mAh, and uses nickel hydroxide powder coated with a cobalt compound having a valence of 2 and nickel oxyhydroxide powder coated with a cobalt compound having a valence greater than 2. On the other hand, comparative cell E containing nickel hydroxide powder and nickel oxyhydroxide powder coated with a cobalt compound having a valence greater than 2 and comparative cell F using nickel hydroxide powder and cobalt hydroxide powder have discharge capacities of about 1000mAh and 960mAh, respectively.
The reason why the discharge capacity of battery D of the present invention is larger than that of battery F is that battery D of the present invention uses nickel hydroxide powder and nickel oxyhydroxide powder coated with cobalt oxyhydroxide having high conductivity, so that the conductivity of nickel oxyhydroxide coated with cobalt oxyhydroxide is higher than that of nickel hydroxide present in the electrode plate. On the other hand, comparative cell E used cobalt hydroxide as a raw material of cobalt oxyhydroxide included therein, and cobalt oxyhydroxide was used only in the form of powder as a conductive agent. Furthermore, the conductivity of the cobalt oxyhydroxide can be maintained at the final stage of discharge in the vicinity of the nickel oxyhydroxide powder with it, using less conductive agent (cobalt oxyhydroxide) than in battery E. This is probably the reason why the comparative cell E had a smaller discharge capacity than the cell of the present invention.
As described above, the battery D of the present invention can maintain high conductivity at any stage during charge and discharge thereof, and can achieve a high utilization percentage of the active material.
The electrode performance of the present invention is not deteriorated even if a small amount of hydroxide such as zinc, cobalt and cadmium is included in the nickel hydroxide powder or the nickel hydroxide powder having a nickel valence of more than 2. Oxidation of the nickel hydroxide powder can be accomplished chemically or electrochemically to produce a nickel hydroxide powder having a nickel valence greater than 2 or to produce a cobalt compound having a cobalt valence greater than 2.
Also, cobalt oxyhydroxide previously coated on the surface of an active material mainly consisting of nickel oxyhydroxide and an active material mainly consisting of nickel hydroxide can be applied to a nickel hydroxide electrode before the preparation of an alkaline storage battery, which can reduce the amount of a negative active material that does not discharge, making it possible to provide an alkaline storage battery with improved energy density.
Claims (7)
1. Nickel hydroxide positive active material powder for alkaline batteries, characterized by: the nickel hydroxide powder as the main component has a valence of nickel greater than 2.3, and a cobalt compound having a valence of cobalt greater than 2 is formed on the surface thereof.
2. The nickel hydroxide positive active material powder for alkaline batteries according to claim 1, wherein the nickel hydroxide powder has a nickel valence smaller than a cobalt valence of the cobalt compound.
3. The nickel hydroxide positive active material powder for alkaline batteries according to claim 1, wherein the nickel hydroxide powder has a nickel valence of not more than 3.
4. A nickel hydroxide electrode is characterized in that: a powdery positive electrode active material containing nickel hydroxide as a main component, which is a powder containing nickel hydroxide having a valence greater than 2.3 as a main component and on the surface of which a cobalt compound having a valence greater than 2 of cobalt is formed, is held on a three-dimensional porous material.
5. An electrode according to claim 4, wherein the positive electrode active material comprises a first nickel hydroxide powder having on a surface thereof a cobalt compound having a cobalt valence of more than 2 and a nickel valence of not more than 2, and a second nickel hydroxide powder having on a surface thereofa cobalt compound having a cobalt valence of more than 2 and a nickel valence of more than 2;
and wherein the average nickel valence of said first and second nickel hydroxide powders is not less than 2.07.
6. An electrode according to claim 4, wherein the nickel hydroxide powder has an average nickel valence less than an average cobalt valence of the cobalt compound.
7. The electrode according to claim 4, wherein said three-dimensional porous material is a three-dimensional metallic porous material.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13448498 | 1998-04-28 | ||
| JP134484/1998 | 1998-04-28 | ||
| JP134484/98 | 1998-04-28 | ||
| JP09998699A JP3448510B2 (en) | 1998-04-28 | 1999-04-07 | Nickel hydroxide powder for alkaline batteries and nickel hydroxide electrode using the same |
| JP99986/99 | 1999-04-07 | ||
| JP99986/1999 | 1999-04-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1235383A CN1235383A (en) | 1999-11-17 |
| CN1148819C true CN1148819C (en) | 2004-05-05 |
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ID=26441075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991060377A Expired - Lifetime CN1148819C (en) | 1998-04-28 | 1999-04-28 | Nickel hydroxide positive active material for alkali battery and electrode using the same |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US6251538B1 (en) |
| JP (1) | JP3448510B2 (en) |
| CN (1) | CN1148819C (en) |
| FR (1) | FR2778023B1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000113904A (en) * | 1998-10-07 | 2000-04-21 | Matsushita Electric Ind Co Ltd | Alkaline storage battery |
| JP3429741B2 (en) * | 2000-03-24 | 2003-07-22 | 松下電器産業株式会社 | Paste positive electrode for alkaline storage batteries and nickel-metal hydride storage batteries |
| JP3558590B2 (en) * | 2000-07-14 | 2004-08-25 | 松下電器産業株式会社 | Method for producing positive electrode active material for alkaline storage battery |
| US6492062B1 (en) * | 2000-08-04 | 2002-12-10 | The Gillette Company | Primary alkaline battery including nickel oxyhydroxide |
| JP2002121029A (en) * | 2000-10-10 | 2002-04-23 | Tanaka Chemical Corp | Conductive cobalt coated nickel hydroxide and method for manufacturing the same |
| CN1307739C (en) * | 2001-03-05 | 2007-03-28 | 株式会社汤浅 | Method for manufacturing nickel hydrogen battery |
| JP2003068293A (en) * | 2001-08-23 | 2003-03-07 | Hitachi Maxell Ltd | Nonsintered positive electrode, its manufacturing method and alkali storage battery using the positive electrode |
| WO2003021698A1 (en) * | 2001-09-03 | 2003-03-13 | Yuasa Corporation | Nickel electrode material and production method therefor, and nickel electrode and alkaline battery |
| JP2003077469A (en) * | 2001-09-03 | 2003-03-14 | Yuasa Corp | Nickel electrode material, its manufacturing method, nickel electrode and alkaline battery |
| US20070248879A1 (en) * | 2002-08-28 | 2007-10-25 | Durkot Richard E | Alkaline battery including nickel oxyhydroxide cathode and zinc anode |
| US6991875B2 (en) * | 2002-08-28 | 2006-01-31 | The Gillette Company | Alkaline battery including nickel oxyhydroxide cathode and zinc anode |
| US7273680B2 (en) * | 2002-08-28 | 2007-09-25 | The Gillette Company | Alkaline battery including nickel oxyhydroxide cathode and zinc anode |
| US20040076881A1 (en) * | 2002-10-17 | 2004-04-22 | Bowden William L. | Method of making a battery |
| US7435395B2 (en) * | 2003-01-03 | 2008-10-14 | The Gillette Company | Alkaline cell with flat housing and nickel oxyhydroxide cathode |
| US20040248007A1 (en) * | 2003-06-09 | 2004-12-09 | Hiromi Tamakoshi | Positive electrode for alkaline battery and alkaline battery using the same |
| JP4305264B2 (en) * | 2004-04-22 | 2009-07-29 | パナソニック株式会社 | Non-sintered positive electrode for alkaline storage battery and alkaline storage battery |
| JP4736372B2 (en) * | 2004-07-30 | 2011-07-27 | トヨタ自動車株式会社 | Positive electrode active material for alkaline storage battery, positive electrode for alkaline storage battery, and alkaline storage battery |
| CN101080831B (en) * | 2004-12-17 | 2011-06-15 | 株式会社杰士汤浅国际 | Alkaline secondary battery-use nickel electrode and production method therefor and alkaline secondary battery |
| JP5610010B2 (en) * | 2012-10-25 | 2014-10-22 | 住友金属鉱山株式会社 | Coated nickel hydroxide powder for positive electrode active material of alkaline secondary battery and method for producing the same |
| CN111295360A (en) * | 2017-11-21 | 2020-06-16 | 株式会社Lg化学 | Positive active material precursor, method for preparing same, and positive active material, positive electrode and secondary battery prepared using same |
| CN112993240B (en) * | 2019-12-17 | 2022-06-10 | 惠州比亚迪电池有限公司 | Positive electrode material, preparation method thereof, positive plate and lithium ion battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE68917045T2 (en) * | 1988-07-19 | 1995-03-16 | Yuasa Battery Co Ltd | Nickel electrode for an alkaline battery. |
| DE69014183T2 (en) * | 1989-09-18 | 1995-06-22 | Toshiba Kawasaki Kk | Nickel-metal hydride secondary cell. |
| US5861225A (en) * | 1992-11-12 | 1999-01-19 | Ovonic Battery Company, Inc. | Nickel battery electrode having multiple composition nickel hydroxide active materials |
| JP3617203B2 (en) * | 1996-07-04 | 2005-02-02 | 松下電器産業株式会社 | Manufacturing method of nickel metal hydride secondary battery |
| JP4366722B2 (en) * | 1997-09-11 | 2009-11-18 | 株式会社ジーエス・ユアサコーポレーション | Nickel hydroxide active material for alkaline storage battery |
| JP3433076B2 (en) * | 1997-11-05 | 2003-08-04 | 三洋電機株式会社 | Non-sintered nickel electrode for sealed alkaline storage batteries |
-
1999
- 1999-04-07 JP JP09998699A patent/JP3448510B2/en not_active Expired - Fee Related
- 1999-04-28 CN CNB991060377A patent/CN1148819C/en not_active Expired - Lifetime
- 1999-04-28 US US09/301,127 patent/US6251538B1/en not_active Expired - Lifetime
- 1999-04-28 FR FR9905352A patent/FR2778023B1/en not_active Expired - Fee Related
-
2001
- 2001-05-10 US US09/851,912 patent/US6558842B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2778023A1 (en) | 1999-10-29 |
| CN1235383A (en) | 1999-11-17 |
| JP2000021401A (en) | 2000-01-21 |
| US20010031400A1 (en) | 2001-10-18 |
| US6251538B1 (en) | 2001-06-26 |
| FR2778023B1 (en) | 2001-05-18 |
| US6558842B2 (en) | 2003-05-06 |
| JP3448510B2 (en) | 2003-09-22 |
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